TWI711053B - Conductive paste, electronic parts and multilayer ceramic capacitors - Google Patents
Conductive paste, electronic parts and multilayer ceramic capacitors Download PDFInfo
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- TWI711053B TWI711053B TW106106596A TW106106596A TWI711053B TW I711053 B TWI711053 B TW I711053B TW 106106596 A TW106106596 A TW 106106596A TW 106106596 A TW106106596 A TW 106106596A TW I711053 B TWI711053 B TW I711053B
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- mass
- conductive paste
- parts
- powder
- acid
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- 239000003985 ceramic capacitor Substances 0.000 title description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 145
- 239000000843 powder Substances 0.000 claims abstract description 94
- 239000002253 acid Substances 0.000 claims abstract description 83
- 239000000919 ceramic Substances 0.000 claims abstract description 65
- 239000003960 organic solvent Substances 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
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- -1 for example Inorganic materials 0.000 description 12
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- 238000000034 method Methods 0.000 description 10
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- 229910002113 barium titanate Inorganic materials 0.000 description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 5
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- 239000001856 Ethyl cellulose Substances 0.000 description 3
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- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 description 3
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
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- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
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Abstract
本發明提供一種接著強度極為優異之導電性糊等。 The present invention provides a conductive paste and the like with extremely excellent bonding strength.
本發明所提供之導電性糊等係包含導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂及有機溶劑之導電性糊，分散劑係包含分子量500以下之酸系分散劑，酸系分散劑係具有含1個以上之分支鏈的分支烴基。 The conductive paste provided by the present invention is a conductive paste containing conductive powder, ceramic powder, dispersant, binder resin, and organic solvent. The dispersant includes an acid dispersant with a molecular weight of 500 or less. Have a branched hydrocarbon group containing more than one branched chain.
Description
本發明係有關導電性糊、電子零件及積層陶瓷電容器。 The present invention relates to conductive paste, electronic parts, and multilayer ceramic capacitors.
隨著行動電話及數位機器等之電子機器的小型化及高性能化，即使對於包含積層陶瓷電容器等之電子零件，亦期待著小型化及高容量化。積層陶瓷電容器係具有複數的介電質層與複數的內部電極層交替積層的構造，藉由將該等的介電質層及內部電極層進行薄膜化，即可實現小型化及高容量化。 With the miniaturization and higher performance of electronic devices such as mobile phones and digital devices, even for electronic components including multilayer ceramic capacitors, miniaturization and higher capacity are expected. Multilayer ceramic capacitors have a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By thinning these dielectric layers and internal electrode layers, miniaturization and high capacity can be achieved.
積層陶瓷電容器係如下述方式製造。首先，在含有鈦酸鋇(BaTiO3)等之介電質粉末及黏合劑樹脂之介電質生片(green sheet)的表面上，將包含導電性粉末及黏合劑樹脂與有機溶劑等之內部電極用糊，以既定之電極圖案印刷者，藉由多層的積層，可得到內部電極與介電質生片之多層積層的積層體。其次，將該積層體加熱壓接而一體化，形成壓接體。將該壓接體切斷，在氧化性環境或惰性氣體環境中進行有機黏合劑脫除處理後，進行燒成，得到燒成晶片(chip)。接著，在燒成晶片之兩端部塗布外部電極用糊，燒成後，在外部電極表面施行鍍鎳等，可得到積層陶瓷電容器。 The multilayer ceramic capacitor is manufactured as follows. First, on the surface of a dielectric green sheet containing a dielectric powder such as barium titanate (BaTiO 3 ) and a binder resin, the inside of the green sheet containing conductive powder, binder resin, and organic solvent If the electrode paste is printed with a predetermined electrode pattern, a multilayer laminate of internal electrodes and dielectric green sheets can be obtained by laminating multiple layers. Next, the laminated body is heated and pressure-bonded and integrated to form a pressure-bonded body. The pressure-bonded body is cut, an organic binder removal treatment is performed in an oxidizing atmosphere or an inert gas atmosphere, and then fired to obtain a fired chip. Next, the external electrode paste is applied to both ends of the fired wafer, and after firing, nickel plating or the like is applied to the surface of the external electrodes to obtain a multilayer ceramic capacitor.
內部電極層之形成所使用的導電性糊係有容易經時性增加黏度之問題。因此，印刷當時係可用所要的黏度在陶瓷生片上以既定厚度形成，惟經既定時間後便會增加黏度，會有以印刷當時的印刷條件而無法形成相同厚度之情形。 The conductive paste used in the formation of the internal electrode layer has a problem that the viscosity tends to increase over time. Therefore, at the time of printing, the desired viscosity can be formed on the ceramic green sheet with a predetermined thickness, but after a predetermined time, the viscosity will increase, and there may be cases where the same thickness cannot be formed under the printing conditions at the time of printing.
因此，試圖改善導電性糊的經時性黏度特性。例如，有報告指出：藉由選擇導電性糊中之黏合劑樹脂或有機溶劑之種類、調配比例等而改善黏度特性。例如，專利文獻1中記載：藉由組合作為黏合劑樹脂之包含疏水性乙基羥基乙基纖維素衍生物的有機載體與特定之有機溶劑，不會導致片衝擊(sheet attack)，為經時變化小之導電性糊。 Therefore, attempts have been made to improve the temporal viscosity characteristics of the conductive paste. For example, there are reports that improve the viscosity characteristics by selecting the type and mixing ratio of the binder resin or organic solvent in the conductive paste. For example, Patent Document 1 describes that by combining an organic vehicle containing a hydrophobic ethyl hydroxyethyl cellulose derivative as a binder resin and a specific organic solvent, it does not cause a sheet attack (sheet attack). Conductive paste with small changes.
而且，專利文獻2中記載：在組合使用包含丁醛樹脂之厚度5μm之陶瓷生片的條件下，含有導電性粉末與有機載體，而該有機載體中之溶劑係以乙酸松香酯為主成分之經時性黏度變化少之導電性糊。 In addition, Patent Document 2 describes that a ceramic green sheet with a thickness of 5 μm containing butyraldehyde resin is used in combination, containing conductive powder and an organic vehicle, and the solvent in the organic vehicle is mainly composed of rosin acetate Conductive paste with little change in viscosity over time.
另一方面，內部電極用所使用之導電性糊係有包含用以提高導電性粉末等之分散性的分散劑者(例如：專利文獻3等)。隨著近年來的內部電極層之薄膜化，導電性粉末之粒徑有變小之傾向。導電性粉末之粒徑小時，該粒子表面之比表面積變大，因此會有導電性粉末(金屬粉末)之表面活性變高、分散性降低、黏度特性降低之情形發生。 On the other hand, the conductive paste used for internal electrodes contains a dispersant for improving the dispersibility of conductive powder and the like (for example, Patent Document 3, etc.). With the thinning of the internal electrode layer in recent years, the particle size of the conductive powder tends to become smaller. When the particle size of the conductive powder is small, the specific surface area of the particle surface becomes larger. Therefore, the surface activity of the conductive powder (metal powder) becomes higher, the dispersibility decreases, and the viscosity characteristics decrease.
例如：專利文獻4中記載一種具有良好的分散性與黏度安定性之導電性糊，其至少含有金屬成分、 氧化物、分散劑及黏合劑樹脂之導電性糊，其中該金屬成分，其表面組成係具有特定之組成比的鎳粉末，分散劑之酸點量係500~2000μmol/g，黏合劑樹脂之酸點量係15~100μmol/g。 For example: Patent Document 4 describes a conductive paste with good dispersibility and viscosity stability, which contains at least metal components, Conductive paste of oxide, dispersant and binder resin. The surface composition of the metal component is nickel powder with a specific composition ratio. The acid point of the dispersant is 500~2000μmol/g. The acid of the binder resin Point weight is 15~100μmol/g.
專利文獻1 日本特開2011-159393號公報 Patent Document 1 JP 2011-159393 A
專利文獻2 日本特開2006-12690號公報 Patent Document 2 JP 2006-12690 A
專利文獻3 日本特開2012-77372號公報 Patent Document 3 JP 2012-77372 A
專利文獻4 日本特開2015-216244號公報 Patent Document 4 JP 2015-216244 A
專利文獻1~4中記載一種經時性黏度變化少之導電性糊。然而，導電性糊之經時性增黏，會隨著內部電極層之薄膜化而使問題更為明顯，因此，隨著近年來之電極圖案的薄膜化而要求經進一步改善過黏度特性的導電性糊。 Patent Documents 1 to 4 describe a conductive paste with little change in viscosity over time. However, the time-dependent increase in the viscosity of the conductive paste will make the problem more obvious as the internal electrode layer becomes thinner. Therefore, with the thinning of the electrode pattern in recent years, it is required to further improve the conductivity of the over-viscosity characteristics. Silly.
本發明之目的係因鑑於如此狀況，提供一種經時性黏度變化極少，黏度安定性更為優異之導電性糊。 The purpose of the present invention is to provide a conductive paste with little change in viscosity over time and with more excellent viscosity stability in view of this situation.
本發明之第1態樣係提供一種導電性糊，其係包含導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂及有機溶劑之導電性糊，其中，分散劑係包含分子量500以下之酸系分散劑，酸系分散劑係具有含1個以上之分支鏈的分支烴基。 The first aspect of the present invention provides a conductive paste comprising conductive powder, ceramic powder, dispersant, binder resin and organic solvent, wherein the dispersant contains an acid with a molecular weight of 500 or less Dispersants, acid-based dispersants have branched hydrocarbon groups containing one or more branched chains.
酸系分散劑係以具有羧基之酸系分散劑者為佳。酸系分散劑係以下述通式(1)所示者為佳。 The acid dispersant is preferably an acid dispersant having a carboxyl group. The acid-based dispersant is preferably one represented by the following general formula (1).
而且，上述通式(1)中，R1係碳數10以上20以下之分支烷基或碳數10以上20以下之分支烯基。 In addition, in the above general formula (1), R 1 is a branched alkyl group having 10 or more and 20 carbon atoms or a branched alkenyl group having 10 or more and 20 carbon atoms.
而且，相對於上述導電性粉末100質量份，酸系分散劑之含量係以0.01質量份以上3質量份以下者為佳。而且，分散劑係以進一步包含鹼系分散劑者為佳。相對於導電性粉末100質量份，分散劑之含量係以0.01質量份以上3質量份以下者為佳。導電性粉末係以包含選自鎳、鈀、鉑、金、銀、銅及該等之合金的至少1種之金屬粉末者為佳。導電性粉末係以平均粒徑0.05μm以上1.0μm以下者為佳。陶磁粉末係以包含鈣鈦礦型氧化物者為佳。陶磁粉末係以平均粒徑0.01μm以上0.5μm以下者為佳。黏合劑樹脂係以包含纖維素系樹脂、丙烯酸系樹脂及丁醛系樹脂中之至少1種者為佳。當將導電性糊在製造完成時之黏度設為100%時，靜置60天後之黏度係以80%以上120%以下者為佳。而且，上述導電性糊係以積層陶磁零件之內部電極用者為佳。 Moreover, the content of the acid-based dispersant is preferably 0.01 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the above-mentioned conductive powder. In addition, the dispersant system preferably further contains an alkaline dispersant. The content of the dispersant is preferably 0.01 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the conductive powder. The conductive powder preferably contains at least one metal powder selected from nickel, palladium, platinum, gold, silver, copper, and alloys thereof. The conductive powder preferably has an average particle size of 0.05 μm or more and 1.0 μm or less. The ceramic powder is preferably one containing perovskite type oxide. The ceramic powder preferably has an average particle size of 0.01 μm or more and 0.5 μm or less. The binder resin system preferably contains at least one of cellulose resin, acrylic resin, and butyraldehyde resin. When the viscosity of the conductive paste at the completion of manufacturing is set to 100%, the viscosity after standing for 60 days is preferably 80% or more and 120% or less. Furthermore, the above-mentioned conductive paste is preferably used for internal electrodes of laminated ceramic parts.
本發明之第2態樣係提供一種電子零件，其係使用上述導電性糊形成者。 The second aspect of the present invention provides an electronic component formed by using the above-mentioned conductive paste.
本發明之第3態樣係提供一種積層陶磁電容器，其至少具有積層有介電質層與內部電極之積層體，上述內部電極係使用上述導電性糊形成者。 A third aspect of the present invention provides a multilayer ceramic capacitor having at least a multilayer body in which a dielectric layer and an internal electrode are laminated, and the internal electrode is formed using the conductive paste.
本發明之導電性糊係經時性黏度變化極少，黏度安定性更為優異。而且，使用本發明之導電性糊形成之積層陶磁電容器等的電子零件之電極圖案在形成薄膜化之電極時，亦使導電性糊之印刷性優異，具有精確均勻的寬度及厚度。 The conductive paste of the present invention has very little change in viscosity over time and has more excellent viscosity stability. Moreover, when the electrode pattern of electronic parts such as multilayer ceramic capacitors formed using the conductive paste of the present invention is formed into thin-film electrodes, the conductive paste also has excellent printability and has a precise and uniform width and thickness.
1‧‧‧積層陶瓷電容器 1.‧‧Multilayer ceramic capacitors
10‧‧‧陶瓷積層體 10‧‧‧Ceramic laminated body
11‧‧‧內部電極層 11‧‧‧Internal electrode layer
12‧‧‧介電質層 12‧‧‧Dielectric layer
20‧‧‧外部電極 20‧‧‧External electrode
21‧‧‧外部電極層 21‧‧‧External electrode layer
22‧‧‧鍍敷層 22‧‧‧Plating layer
圖1係呈示實施形態之積層陶磁電容器的透視圖及剖視圖。 Fig. 1 is a perspective view and a cross-sectional view showing the multilayer ceramic capacitor of the embodiment.
本實施形態之導電性糊係包含導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂及有機溶劑。以下，對於各成分進行詳細說明。 The conductive paste of this embodiment includes conductive powder, ceramic powder, dispersant, binder resin, and organic solvent. Hereinafter, each component will be described in detail.
導電性粉末並無特別限定，可使用例如：選自鎳、鈀、鉑、金、銀、銅及該等之合金的至少1種之粉末。該等之中，由導電性、耐腐蝕性及成本之觀點來看，以鎳或其合金之粉末為佳。鎳合金方面，係可使用例如：選自錳、鉻、鈷、鋁、鐵、銅、鋅、銀、金、鉑及鈀所成組群之至少1種以上的元素與鎳之合金。鎳合 金中之鎳含量係例如：50質量%以上，以80質量%以上為佳。而且，鎳粉末在去黏合劑處理時，抑制黏合劑樹脂因部分熱分解之快速氣體的產生，故可包含數百ppm左右之S。 The conductive powder is not particularly limited, and for example, at least one powder selected from nickel, palladium, platinum, gold, silver, copper, and alloys thereof can be used. Among them, from the viewpoints of conductivity, corrosion resistance, and cost, nickel or its alloy powder is preferred. For nickel alloys, for example, alloys of at least one element selected from the group consisting of manganese, chromium, cobalt, aluminum, iron, copper, zinc, silver, gold, platinum, and palladium and nickel can be used. Nickel The nickel content in gold is, for example, 50% by mass or more, preferably 80% by mass or more. In addition, the nickel powder suppresses the rapid gas generation due to partial thermal decomposition of the binder resin during the debinding process, so it can contain about hundreds of ppm of S.
導電性粉末之平均粒徑係以0.05μm以上1.0μm以下為佳，以0.1μm以上0.5μm以下更佳。導電性粉末之平均粒徑在上述範圍時，可適用作為薄膜化之積層陶磁電容器之內部電極用糊，例如：提高乾燥膜之平滑性及乾燥膜密度。平均粒徑係指經由掃描型電子顯微鏡(SEM)觀察而求得之值，粒度分佈的累積值50%之粒徑。 The average particle size of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.5 μm or less. When the average particle size of the conductive powder is in the above range, it can be used as a paste for the internal electrode of a multilayer ceramic capacitor with thin film, for example, to improve the smoothness and density of the dry film. The average particle size refers to the value obtained through scanning electron microscope (SEM) observation, and the particle size is 50% of the cumulative value of the particle size distribution.
導電性粉末之含量，相對於導電性糊之總量，係以30質量%以上70質量%以下為佳，以40質量%以上65質量%以下更佳。導電性粉末之含量在上述範圍時，導電性及分散性優異。 The content of the conductive powder relative to the total amount of the conductive paste is preferably 30% by mass to 70% by mass, and more preferably 40% by mass to 65% by mass. When the content of the conductive powder is in the above range, conductivity and dispersibility are excellent.
陶磁粉末方面，並無特別限定，例如，為積層陶磁電容器之內部電極用糊時，可依適用的積層陶磁電容器之種類而適當地選擇習知的陶磁粉末。陶磁粉末方面，可列舉例如：包含鋇及鈦之鈣鈦礦型氧化物，以鈦酸鋇(BaTiO3)為佳。而且，陶磁粉末係可使用1種，亦可使用2種以上。 The ceramic powder is not particularly limited. For example, when it is a paste for the internal electrodes of a multilayer ceramic capacitor, a conventional ceramic powder can be appropriately selected according to the type of the applicable multilayer ceramic capacitor. As for the ceramic powder, for example, perovskite-type oxides containing barium and titanium can be cited, and barium titanate (BaTiO 3 ) is preferred. Furthermore, one type of ceramic powder system may be used, or two or more types may be used.
陶磁粉末方面，係可使用包含以鈦酸鋇為主成分以及以氧化物為副成分之陶磁粉末。氧化物方面，係可列舉如：由選自錳、鉻、矽、鈣、鋇、鎂、釩、鎢、鉭、鈮及稀土元素之1種以上所成的氧化物。 For ceramic powder, ceramic powder containing barium titanate as the main component and oxide as the secondary component can be used. As for the oxides, for example, oxides made of one or more selected from the group consisting of manganese, chromium, silicon, calcium, barium, magnesium, vanadium, tungsten, tantalum, niobium and rare earth elements.
而且，陶磁粉末方面，可列舉例如：鈦酸鋇(BaTiO3)之鋇原子或鈦原子，以其它原子，例如：以錫、鉛、鋯等取代之鈣鈦礦型氧化物的強介電質之陶磁粉末。 In addition, ceramic powders include, for example, barium or titanium atoms of barium titanate (BaTiO 3 ), and other atoms, such as ferroelectrics of perovskite-type oxides substituted with tin, lead, zirconium, etc. The ceramic powder.
內部電極用糊中之陶磁粉末方面，係可使用與構成積層陶磁電容器之生片的介電質陶磁粉末相同組成的粉末。藉此，可抑制因燒結步驟中之介電質層與內部電極層之界面間的收縮之錯配(mismatch)所產生的龜裂。如此之陶磁粉末方面，除了上述之包含鋇及鈦之鈣鈦礦型氧化物以外，可列舉例如：氧化鋅、肥粒鐵、PZT、氧化鋇、氧化鋁、氧化鉍、R(稀土元素)2O3、氧化鈦、氧化釹等之氧化物。 As for the ceramic powder in the internal electrode paste, it is possible to use powder with the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor. Thereby, it is possible to suppress the cracks caused by the mismatch of the shrinkage between the dielectric layer and the internal electrode layer in the sintering step. For such ceramic powders, in addition to the above-mentioned perovskite-type oxides containing barium and titanium, for example, zinc oxide, ferrite, PZT, barium oxide, aluminum oxide, bismuth oxide, R (rare earth element) 2 O 3 , titanium oxide, neodymium oxide and other oxides.
陶磁粉末之平均粒徑係例如：0.01μm以上0.5μm以下，較佳為以0.01μm以上0.3μm以下之範圍。藉由陶磁粉末之平均粒徑在上述範圍，則作為內部電極用糊使用時，可形成充分細、薄且均一的內部電極。平均粒徑係指經由掃描型電子顯微鏡(SEM)觀察而求得之值，粒度分佈的累積值50%之粒徑。 The average particle size of the ceramic powder is, for example, 0.01 μm or more and 0.5 μm or less, preferably in the range of 0.01 μm or more and 0.3 μm or less. When the ceramic powder has an average particle size in the above range, when used as a paste for internal electrodes, a sufficiently fine, thin, and uniform internal electrode can be formed. The average particle size refers to the value obtained through scanning electron microscope (SEM) observation, and the particle size is 50% of the cumulative value of the particle size distribution.
陶磁粉末之含量，相對於導電性粉末100質量份，係以1質量份以上30質量份以下為佳，以3質量份以上30質量份以下更佳。 The content of the ceramic powder is preferably not less than 1 part by mass and not more than 30 parts by mass relative to 100 parts by mass of the conductive powder, and more preferably not less than 3 parts by mass and not more than 30 parts by mass.
陶磁粉末之含量，相對於導電性糊之總量，係以1質量%以上20質量%以下為佳，以3質量%以上20質量%以下更佳。導電性粉末之含量在上述範圍時，導電性及分散性優異。 The content of the ceramic powder relative to the total amount of the conductive paste is preferably 1% by mass to 20% by mass, and more preferably 3% by mass to 20% by mass. When the content of the conductive powder is in the above range, conductivity and dispersibility are excellent.
黏合劑樹脂方面，並無特別限定，可使用習知的樹脂。黏合劑樹脂方面，係可列舉例如：甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、硝基纖維素等之纖維素系樹脂、丙烯酸系樹脂、聚乙烯丁醛等之丁醛系樹脂等。其中，由對於溶劑之溶解性、燃燒分解性之觀點等來說，係以包含乙基纖維素者為佳。而且，作為內部電極用糊使用時，由提高與生片之接著強度之觀點來看，可包含丁醛樹脂、或可僅以丁醛樹脂使用。黏合劑樹脂可使用1種，或使用2種以上。而且，黏合劑樹脂之分子量係例如：20000~200000左右。 The binder resin is not particularly limited, and conventional resins can be used. As for the binder resin, for example, cellulose resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, acrylic resins, polyvinyl butyral, etc. Aldehyde resin etc. Among them, from the viewpoint of solvent solubility and combustion decomposability, it is preferable to include ethyl cellulose. Furthermore, when used as a paste for internal electrodes, from the viewpoint of improving the adhesive strength with the green sheet, butyral resin may be included, or only butyral resin may be used. One type of binder resin can be used, or two or more types can be used. Moreover, the molecular weight of the adhesive resin is, for example, about 20,000 to 200,000.
相對於導電性粉末100質量份，黏合劑樹脂之含量係以1質量份以上10質量份以下為佳，以1質量份以上8質量份以下更佳。 Relative to 100 parts by mass of the conductive powder, the content of the binder resin is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less.
相對於導電性糊之總量，黏合劑樹脂之含量，係以0.5質量%以上10質量%以下為佳，以1質量%以上6質量%以下更佳。黏合劑樹脂之含量在上述範圍時，導電性及分散性優異。 The content of the binder resin relative to the total amount of the conductive paste is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 6% by mass. When the content of the binder resin is in the above range, conductivity and dispersibility are excellent.
有機溶劑方面，並無特別限定，可使用可溶解上述黏合劑樹脂之習知的有機溶劑。有機溶劑方面，係可列舉例如：二氫乙酸松香酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯、異丁酸異莰酯、乙二醇單丁基醚乙酸酯、二丙二醇甲基醚乙酸酯等之乙酸酯系溶劑；萜品醇、二氫萜品醇等之萜烯系溶劑；十三烷、壬烷及環己 烷等之飽合脂肪族烴溶劑等。而且，有機溶劑係可使用1種，或使用2種以上。 The organic solvent is not particularly limited, and a conventional organic solvent that can dissolve the above-mentioned binder resin can be used. In terms of organic solvents, for example, rosin dihydroacetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, Acetate-based solvents such as dipropylene glycol methyl ether acetate; terpene-based solvents such as terpineol and dihydroterpineol; tridecane, nonane and cyclohexane Saturated aliphatic hydrocarbon solvents such as alkanes. Moreover, the organic solvent system can use 1 type or 2 or more types.
有機溶劑係可包含例如：選自二氫乙酸松香酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯等之至少1種的乙酸酯系溶劑(A)。該等之中，以乙酸異莰酯更佳。當有機溶劑包含以乙酸酯系溶劑(A)作為主成分時，相對於有機溶劑全部，乙酸酯系溶劑(A)之含量以90質量%以上100質量%以下為佳，以含有100質量%更佳。 The organic solvent may include, for example, at least one acetate solvent selected from the group consisting of rosin dihydroacetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. A). Among these, isobornyl acetate is more preferred. When the organic solvent contains the acetate-based solvent (A) as the main component, relative to the total organic solvent, the content of the acetate-based solvent (A) is preferably 90% by mass or more and 100% by mass or less, with 100% by mass % Is better.
而且，有機溶劑係可包含例如：上述乙酸酯系溶劑(A)與選自乙二醇單丁基醚乙酸酯、二丙二醇甲基醚乙酸酯之至少1種的乙酸酯系溶劑(B)。使用如此之混合溶劑時，可容易地進行導電性糊的黏度調整，可加快導電性糊之乾燥速度。 Furthermore, the organic solvent may include, for example, the above-mentioned acetate solvent (A) and at least one acetate solvent selected from the group consisting of ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate (B). When using such a mixed solvent, the viscosity of the conductive paste can be adjusted easily, and the drying speed of the conductive paste can be accelerated.
如為包含乙酸酯系溶劑(A)與乙酸酯系溶劑(B)之混合液的情形下，相對於有機溶劑全部，有機溶劑係以乙酸酯系溶劑(A)之含量為50質量%以上90質量%以下為佳，以60質量%以上80質量%以下更佳。如為上述混合液，相對於有機溶劑全部100質量%，有機溶劑係以乙酸酯系溶劑(B)之含量為10質量%以上50質量%以下為佳，以20質量%以上40質量%以下更佳。 In the case of a mixed liquid containing an acetate-based solvent (A) and an acetate-based solvent (B), the content of the acetate-based solvent (A) in the organic solvent is 50 mass relative to all organic solvents % Or more and 90 mass% or less is preferable, more preferably 60 mass% or more and 80 mass% or less. If it is the above mixed liquid, relative to 100% by mass of the organic solvent, the content of the acetate solvent (B) is preferably 10% by mass or more and 50% by mass or less, and 20% by mass or more and 40% by mass or less Better.
相對於導電性粉末100質量份，有機溶劑之含量係以40質量份以上90質量份以下為佳，以45質量份以上85質量份以下更佳。有機溶劑之含量在上述範圍時，導電性及分散性優異。 Relative to 100 parts by mass of the conductive powder, the content of the organic solvent is preferably 40 parts by mass or more and 90 parts by mass or less, and more preferably 45 parts by mass or more and 85 parts by mass or less. When the content of the organic solvent is in the above range, conductivity and dispersibility are excellent.
相對於導電性糊之總量，有機溶劑之含量係以20質量%以上50質量%以下為佳，以25質量%以上45質量%以下更佳。有機溶劑之含量在上述範圍時，導電性及分散性優異。 Relative to the total amount of the conductive paste, the content of the organic solvent is preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 45% by mass. When the content of the organic solvent is in the above range, conductivity and dispersibility are excellent.
本實施形態之導電性糊係包含具有分支烴基之酸系分散劑。該酸系分散劑之分支烴基係具有1個以上之分支鏈。本發明者等對於導電性糊中使用的分散劑，對各種分散劑進行各種研究之結果，發現藉由包含具有分支烴基之酸系分散劑，其理由雖不清楚，惟導電性糊之經時性黏度變化受到抑制頗多。 The conductive paste of this embodiment contains an acid-based dispersant having a branched hydrocarbon group. The branched hydrocarbon group of the acid-based dispersant has more than one branched chain. The inventors of the present invention conducted various studies on various dispersants for dispersants used in conductive pastes, and found that by including acid-based dispersants having branched hydrocarbon groups, the reason is not clear, but the conductive paste has time The change in viscosity is suppressed a lot.
而且，酸系分散劑係以具有羧基者為佳。藉由使用如此之分散劑，其原因雖不限定，惟推斷是羧基吸附在導電性粉末等的表面，將表面電位中和、或使氫鍵部位失活，羧基以外之部位之上述般的特定之立體構造，係有效地抑制導電性粉末等之凝集而可進一步提高糊黏度之安定性。而且，該酸系分散劑可為具有醯胺鍵之化合物。 Moreover, the acid-based dispersant is preferably one having a carboxyl group. By using such a dispersant, the reason is not limited, but it is presumed that the carboxyl group is adsorbed on the surface of conductive powder etc. to neutralize the surface potential or deactivate the hydrogen bond site, and the site other than the carboxyl group is specified as described above The three-dimensional structure effectively inhibits the aggregation of conductive powders, etc., and can further improve the stability of the paste viscosity. Furthermore, the acid-based dispersant may be a compound having an amide bond.
而且，上述酸系分散劑係以低分子量者為佳。此處，低分子量之酸系分散劑係指例如分子量為500以下之顯示酸性的分散劑。另一方面，分子量之下限係以100以上為佳，以200以上更佳。另外，上述分散劑係可使用1種，亦可使用2種以上。 Furthermore, the above-mentioned acid-based dispersing agent is preferably one having a low molecular weight. Here, the low-molecular-weight acid-based dispersant refers to, for example, a dispersant exhibiting acidity with a molecular weight of 500 or less. On the other hand, the lower limit of the molecular weight is preferably 100 or more, more preferably 200 or more. Moreover, the said dispersing agent system may use 1 type, and may use 2 or more types.
例如：酸系分散劑中之烴基在主鏈可包含1個分支鏈，亦可包含2個以上之分支鏈。分支鏈之數係以1以上3以下為佳。而且，分支鏈之數可為4以上。 For example, the hydrocarbyl group in the acid-based dispersant may include one branched chain in the main chain, or two or more branched chains. The number of branch chains is preferably 1 or more and 3 or less. Furthermore, the number of branch chains may be 4 or more.
酸系分散劑可為包含具有分支位置不同的分支烴基之複數的酸系分散劑之混合物。如為包含複數的酸系分散劑之混合物，可進一步提高經時性的糊黏度安定性。 The acid-based dispersant may be a mixture containing a plurality of acid-based dispersants having branched hydrocarbon groups with different branch positions. If it is a mixture containing a plurality of acid-based dispersants, the viscosity stability of the paste over time can be further improved.
而且，酸系分散劑可為具有複雜的分支構造(例如分支鏈為2以上)之酸系分散劑。如為具有如此的複雜之分支構造的酸系分散劑，可進一步提高經時性的糊黏度安定性。 Furthermore, the acid-based dispersant may be an acid-based dispersant having a complicated branched structure (for example, the branched chain is 2 or more). If it is an acid-based dispersant having such a complicated branched structure, the viscosity stability of the paste over time can be further improved.
作為如此之酸系分散劑，可列舉例如：下述通式(1)所示之酸系分散劑。 Examples of such acid-based dispersants include acid-based dispersants represented by the following general formula (1).
上述之通式(1)中，R1表示碳數10以上20以下之分支烷基(或是碳數10以上20以下之分支烯基)。R1係以碳數15以上20以下為佳，以碳數17以上更佳。而且，R1可為分支烷基，亦可為具有碳雙鍵的分支烯基，以分支烷基為佳。 In the above general formula (1), R 1 represents a branched alkyl group having a carbon number of 10 or more and 20 or less (or a branched alkenyl group having a carbon number of 10 or more and 20 or less). R 1 preferably has a carbon number of 15 or more and 20 or less, and more preferably a carbon number of 17 or more. In addition, R 1 may be a branched alkyl group or a branched alkenyl group having a carbon double bond, preferably a branched alkyl group.
而且，分支鏈之有無係可透過例如依據13C-NMR或1H-NMR之質譜而計算出的烴基之末端的甲基(-CH3)之含有比例來進行確認。而且，上述通式(1)所示之酸系分散劑為混合物的情況時、或通式(1)中之R1 的構造為具有複數之分支的複雜構造的情況等時，可為未檢測出顯現R1部分之明確波峰。即使在該情況下，仍可明確地觀察到顯現末端之甲基(-CH3)的波峰。 In addition, the presence or absence of a branched chain can be confirmed by, for example, the content ratio of the methyl group (-CH 3 ) at the end of the hydrocarbon group calculated from the mass spectrum of 13 C-NMR or 1 H-NMR. Moreover, when the acid-based dispersant represented by the above general formula (1) is a mixture, or when the structure of R 1 in the general formula (1) is a complicated structure with plural branches, it may be undetected A clear peak appears in the R 1 part. Even in this case, a peak showing the methyl group (-CH 3 ) at the end can be clearly observed.
相對於導電性粉末100質量份，上述酸系分散劑係以含有0.01質量份以上3質量份以下為佳，以含有0.05質量份以上2質量份以下更佳，含有0.05質量份以上1質量份以下又更佳。酸系分散劑之含量在上述範圍時，導電性糊中之導電性粉末的分散性，及導電性糊之經時性黏度的安定性優異。 Relative to 100 parts by mass of the conductive powder, the acid-based dispersant system preferably contains 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 2 parts by mass or less, and 0.05 parts by mass or more and 1 part by mass or less Better yet. When the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder in the conductive paste and the stability of the temporal viscosity of the conductive paste are excellent.
尤其是，由進一步提高經時性黏度之安定性的觀點來說，相對於導電性粉末100質量份，上述酸系分散劑含量係以0.5質量份以上2質量份以下為佳，以1質量份以上2質量份以下更佳。而且，由所謂導電性之提高、或抑制片衝擊之觀點來看，上述酸系分散劑之含量係以少者為佳，上述酸系分散劑之含量的上限可為例如：1質量份以下，以0.5質量份以下為佳。本實施型態之導電性糊，例如上述酸系分散劑之含量即使為0.1質量份以上0.5質量份以下，經時性黏度的安定性亦為優異。 In particular, from the viewpoint of further improving the stability of the viscosity with time, relative to 100 parts by mass of the conductive powder, the content of the acid-based dispersant is preferably 0.5 parts by mass or more and 2 parts by mass or less, and 1 part by mass The above 2 parts by mass or less is more preferable. Moreover, from the viewpoint of improving conductivity or suppressing sheet impact, the content of the acid-based dispersant is preferably less. The upper limit of the content of the acid-based dispersant can be, for example, 1 part by mass or less, It is preferably 0.5 parts by mass or less. The conductive paste of this embodiment, for example, even if the content of the acid-based dispersant is 0.1 part by mass or more and 0.5 part by mass or less, the stability of the viscosity over time is excellent.
相對於導電性糊全部，含有上述酸系分散劑例如3質量%以下。上述酸系分散劑之含量上限，係以2質量%以下為佳，以1.5質量%以下更佳，以1質量%以下又更佳。酸系分散劑之含量下限雖無特別限定，例如可為0.01質量%以上，以0.05質量%以上為佳。酸系分散劑之含量在上述範圍時，經時性黏度的變化更為穩定 而受到抑制。而且，有機溶劑之中，當與黏合劑樹脂組合使用時，亦有導致片衝擊或生片之剝離不良者，惟在含有特定量之上述酸系分散劑時，可抑制該等之問題。 The above-mentioned acid-based dispersant is contained, for example, 3% by mass or less with respect to the entire conductive paste. The upper limit of the content of the acid-based dispersant is preferably 2% by mass or less, more preferably 1.5% by mass or less, and more preferably 1% by mass or less. Although the lower limit of the content of the acid-based dispersant is not particularly limited, for example, it may be 0.01% by mass or more, preferably 0.05% by mass or more. When the content of acid-based dispersant is in the above range, the change of viscosity over time is more stable And be restrained. In addition, among organic solvents, when used in combination with a binder resin, there are some that cause sheet impact or green sheet peeling failure. However, when a specific amount of the acid-based dispersant is contained, these problems can be suppressed.
上述酸系分散劑係例如可由市售之製品選擇滿足上述特性者而使用。而且，酸系分散劑係可使用以往習知的製造方法，滿足上述特性之方式而製造。 The acid-based dispersant system can be selected from commercially available products that satisfy the above-mentioned characteristics, for example. Furthermore, the acid-based dispersant system can be manufactured in a manner that satisfies the above-mentioned characteristics using a conventionally known manufacturing method.
導電性糊係可包含上述酸系分散劑以外的分散劑，例如：可含有具有直鏈之烴基的酸系分散劑。如此之上述酸系分散劑以外的酸系分散劑方面，可列舉例如：高級脂肪酸及高分子界面活性劑等之酸系分散劑等。該等分散劑可使用1種或組合2種以上使用。 The conductive paste system may contain a dispersant other than the above-mentioned acid-based dispersant, for example, it may contain an acid-based dispersant having a linear hydrocarbon group. Such acid-based dispersants other than the aforementioned acid-based dispersants include, for example, acid-based dispersants such as higher fatty acids and polymer surfactants. These dispersants can be used 1 type or in combination of 2 or more types.
高級脂肪酸方面，可為不飽和羧酸亦可為飽和羧酸，並無特別限定，惟可列舉如：硬脂酸、油酸、肉荳蔻酸、棕櫚酸、亞麻油酸、月桂酸、亞麻仁油酸等之碳數11以上者。其中，以油酸或硬脂酸為佳。
In terms of higher fatty acids, it may be unsaturated carboxylic acid or saturated carboxylic acid, and is not particularly limited, but examples include: stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, linseed Oleic acid, etc. with
其它以外之酸系分散劑方面，並無特別限定，可列舉如：選自以單烷基胺鹽為代表之烷基單胺鹽型、以N-烷基(C14~C18)丙二胺二油酸鹽為代表之烷基二胺鹽型、以烷基三甲基銨氯化物為代表之烷基三甲基銨鹽型、椰子烷基二甲基苄基銨氯化物為代表之烷基二甲基苄基銨鹽型、烷基/二聚氧乙烯甲基銨氯化物為代表之4級銨鹽型、烷基吡啶鎓鹽型、二甲基硬脂基胺為代表之3級胺型、聚氧丙烯/聚氧乙烯烷基胺為代表之聚氧乙烯烷基胺型、以N,N’,N’-三(2-羥基乙基)-N-烷基(C14~C18)-1,3-二胺基丙烷為代表之二胺的氧乙烯加成型之界面活性劑，該等之中，以烷基單胺鹽型為佳。 There are no particular restrictions on acid-based dispersants other than others. Examples include: alkyl monoamine salt type selected from monoalkylamine salts, N-alkyl (C14~C18) propylene diamine diamine Alkyl diamine salt type represented by oleate, alkyl trimethyl ammonium salt type represented by alkyl trimethyl ammonium chloride, and alkyl group represented by coconut alkyl dimethyl benzyl ammonium chloride Dimethyl benzyl ammonium salt type, alkyl/dipolyoxyethylene methyl ammonium chloride as the representative quaternary ammonium salt type, alkyl pyridinium salt type, and dimethyl stearyl amine as the representative tertiary amine Type, polyoxyethylene alkylamine type represented by polyoxypropylene/polyoxyethylene alkylamine, with N,N',N'-tris(2-hydroxyethyl)-N-alkyl (C14~C18) -1,3-diaminopropane is a surfactant for the oxyethylene addition of diamine as a representative. Among these, the alkyl monoamine salt type is preferred.
烷基單胺鹽型方面，係以使用例如：甘胺酸與油酸之化合物的油醯肌胺酸、以硬脂酸或月桂酸取代油酸等之高級脂肪酸的醯胺化合物為佳。 In terms of the alkyl monoamine salt type, it is preferable to use, for example, oleic sarcosine, which is a compound of glycine and oleic acid, and an amide compound in which higher fatty acids such as stearic acid or lauric acid are substituted for oleic acid.
而且，分散劑可含有酸系分散劑以外之分散劑。酸系分散劑以外之分散劑方面，可列舉如：鹼系分散劑、非離子系分散劑、兩性分散劑等。該等分散劑可使用1種或組合2種以上使用。 Furthermore, the dispersant may contain a dispersant other than an acid-based dispersant. Examples of dispersants other than acid-based dispersants include alkaline dispersants, nonionic dispersants, and amphoteric dispersants. These dispersants can be used 1 type or in combination of 2 or more types.
鹼系分散劑方面，可列舉例如：月桂基胺、松香胺、鯨蠟基胺、肉荳蔻基胺、硬脂基胺等之脂肪族胺等。導電性糊在含有具有上述分支烴基的酸系分散劑與鹼系分散劑時，分散性更為優異，經時性黏度安定性亦為優異。 As for the alkali-based dispersant, for example, aliphatic amines such as lauryl amine, rosin amine, cetyl amine, myristyl amine, and stearyl amine can be mentioned. When the conductive paste contains the acid-based dispersant and the alkali-based dispersant having the above-mentioned branched hydrocarbon group, the dispersibility is more excellent, and the viscosity stability over time is also excellent.
鹼系分散劑係例如，相對於導電性粉末100質量份，可含有0.2質量份以上2.5質量份以下，以含有0.2質量份以上1質量份以下為佳。而且，鹼系分散劑係例如：相對於上述之具有分支烴基的酸系分散劑100質量份，可含有10質量份以上300質量份左右，以50質量份以上150質量份左右為佳。所含鹼系分散劑在上述範圍時，糊的經時性之黏度安定性更為優異。 The alkali-based dispersant system may be contained, for example, from 0.2 part by mass to 2.5 parts by mass, and preferably from 0.2 part by mass to 1 part by mass relative to 100 parts by mass of the conductive powder. Furthermore, the alkaline dispersant system may contain, for example, 10 parts by mass or more and about 300 parts by mass relative to 100 parts by mass of the above-mentioned acid-based dispersant having branched hydrocarbon groups, preferably 50 parts by mass or more and about 150 parts by mass. When the alkali-based dispersant is contained in the above range, the viscosity stability of the paste over time is more excellent.
鹼系分散劑係例如：相對於導電性糊全部，含有0質量%以上2.5質量%以下，以0質量%以上1.0質量%以下為佳，以0.1質量%以上1.0質量%以下更佳，以0.1質量%以上0.8質量%以下又更佳。所含鹼系分散劑在上述範圍時，糊的經時之黏度安定性更為優異。 Alkaline dispersant system, for example: relative to the entire conductive paste, the content is 0% by mass to 2.5% by mass, preferably 0% by mass to 1.0% by mass, more preferably 0.1% by mass to 1.0% by mass, and 0.1 It is more preferably not less than mass% and not more than 0.8 mass%. When the alkali-based dispersant is contained in the above range, the viscosity stability of the paste over time is more excellent.
上述酸系分散劑以外之分散劑係例如，相對於導電性粉末100質量份，可含有0.2質量份以上2.5質量份以下。而且，上述酸系分散劑以外之分散劑係例如，相對於酸系分散劑100質量份，可含有50質量份以上300質量份以下。而且，分散劑全部方面，相對於導電性粉末100質量份，以含有0.01質量份以上3質量份以下為佳。 For example, the dispersant system other than the above-mentioned acid-based dispersant may contain 0.2 parts by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the conductive powder. Furthermore, the dispersant system other than the above-mentioned acid-based dispersant may be contained, for example, from 50 parts by mass to 300 parts by mass relative to 100 parts by mass of the acid-based dispersant. In addition, in all respects, the dispersant preferably contains 0.01 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the conductive powder.
上述酸系分散劑以外之分散劑係例如，相對於導電性糊全部，含有0質量%以上2.5質量%以下，以0質量%以上1.0質量%以下為佳，以0.1質量%以上1.0質量%以下更佳，以0.1質量%以上0.8質量%以下又更佳。酸系分散劑以外之分散劑超出1.0重量%時，導電性糊不僅乾燥性變差，在片衝擊方面亦不佳。 Dispersants other than the above-mentioned acid-based dispersants, for example, relative to the entire conductive paste, the content is 0% by mass to 2.5% by mass, preferably 0% by mass to 1.0% by mass, and 0.1% by mass to 1.0% by mass. More preferably, it is more preferably not less than 0.1% by mass and not more than 0.8% by mass. When the dispersant other than the acid-based dispersant exceeds 1.0% by weight, the conductive paste not only deteriorates in drying properties, but also has poor sheet impact.
本實施型態之導電性糊係可藉由準備上述各成分，以攪拌機進行攪拌/捏合而製造。此時，在導電性粉末表面預先塗布分散劑時，導電性粉末並未凝集而充分鬆開，使分散劑在該表面分散，容易得到均一的導電性糊。而且，亦可使黏合劑樹脂溶解於載體用之有機溶劑中，製作有機載體，對糊用之有機溶劑添加導電性粉末、陶瓷粉末、有機載體及分散劑，再以攪拌機進行攪拌/捏合而製作導電性糊。 The conductive paste of this embodiment can be produced by preparing the above-mentioned components and mixing/kneading with a mixer. At this time, when the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is not aggregated but loosens sufficiently, and the dispersant is dispersed on the surface, and a uniform conductive paste is easily obtained. Moreover, it is also possible to dissolve the binder resin in the organic solvent for the carrier to make an organic carrier, add conductive powder, ceramic powder, organic carrier and dispersant to the organic solvent for the paste, and then stir/knead it with a mixer. Conductive paste.
而且，有機溶劑中，載體用之有機溶劑方面，為了提高與有機載體之融合，以使用與調整導電性糊之黏度的糊用有機溶劑之相同者為佳。載體用之有機溶劑 的含量，相對於導電性粉末100質量份，例如為5質量份以上30質量份以下。而且，導電性糊用之有機溶劑的含量，相對於導電性糊全部量，係以10質量%以上40質量%以下為佳。 In addition, in the organic solvent, the organic solvent for the carrier, in order to improve the fusion with the organic carrier, it is better to use the same organic solvent for the paste that adjusts the viscosity of the conductive paste. Organic solvent for carrier The content of is, for example, 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the conductive powder. Moreover, the content of the organic solvent for the conductive paste is preferably 10% by mass or more and 40% by mass or less with respect to the total amount of the conductive paste.
導電性糊以下述式求得之靜置60天後之黏度，例如為0%以上30%以下，以25%以下為佳，以20%以下更佳。 The viscosity of the conductive paste after 60 days of standing is obtained by the following formula, for example, 0% or more and 30% or less, preferably 25% or less, and more preferably 20% or less.
式：[(靜置60天後之黏度-製造完成時之黏度)/製造完成時之黏度]×100 Formula: [(Viscosity after standing for 60 days-Viscosity when manufacturing is completed)/Viscosity when manufacturing is completed]×100
而且，導電性糊係，導電性糊在製造完成時之黏度設為100%時，靜置60天後之黏度例如為70%以上130%以下，以80%以上120%以下為佳，以85%以上115%以下更佳，以90%以上110%以下又更佳。 In addition, for conductive pastes, when the viscosity of the conductive paste is set to 100% when the manufacturing is completed, the viscosity after 60 days of standing is 70% or more and 130% or less, preferably 80% or more and 120% or less, and 85% More than 115% is more preferred, and more than 90% is more preferably less than 110%.
導電性糊係可適用在積層陶瓷電容器等之電子零件。積層陶瓷電容器係具有使用介電質生片形成之介電質層及使用導電性糊形成之內部電極層。 The conductive paste can be applied to electronic parts such as multilayer ceramic capacitors. Multilayer ceramic capacitors have a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
積層陶瓷電容器係以介電質生片中所含的介電質陶瓷粉末與導電性糊中所含的陶瓷粉末為相同組成之粉末者為佳。使用本實施型態之導電性糊所製造之積層陶瓷元件，即使介電質生片之厚度例如為3μm以下，亦可抑制片衝擊或生片之剝離不良。 The multilayer ceramic capacitor preferably has the same composition as the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste. In the multilayer ceramic device manufactured using the conductive paste of this embodiment, even if the thickness of the dielectric green sheet is 3 μm or less, for example, sheet impact or peeling failure of the green sheet can be suppressed.
以下，對於本發明之電子零件等的實施型態，參照圖式同時進行說明。圖式中，會有適當、模式地表示及變更比例表示之情形。而且，構件之位置及方 向等係適當地參照圖1等所呈示之XYZ正交座標系進行說明。該XYZ正交座標系中，X方向及Y方向為水平方向、Z方向為垂直方向(上下方向)。 Hereinafter, the implementation modes of the electronic components and the like of the present invention will be described with reference to the drawings. In the diagram, there will be situations where the representation is appropriately and modelled and the scale is changed. Moreover, the location and orientation of the components The directional system will be described with reference to the XYZ orthogonal coordinate system shown in FIG. 1 and the like. In this XYZ orthogonal coordinate system, the X direction and the Y direction are the horizontal direction, and the Z direction is the vertical direction (up and down direction).
圖1A及圖1B係表示實施型態之電子零件的一例之積層陶瓷電容器1之圖。積層陶瓷電容器1係具備介電質層12及內部電極層11交替積層之積層體10與外部電極20者。
1A and 1B are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component of an implementation type. The multilayer ceramic capacitor 1 includes a
以下，對於使用上述導電性糊之積層陶瓷電容器的製造方法進行說明。首先，在包含陶瓷生片之介電質層12上，將包含導電性糊之內部電極層11以印刷法形成，將上表面具有該內部電極層之複數個介電質層，使經壓接而積層，得到積層體10之後，將積層體10燒成使一體化，藉此製作成為陶瓷電容器本體之積層陶瓷燒成體(無圖式)。然後，藉由在該陶瓷電容器本體之兩端部形成一對外部電極，製造積層陶瓷電容器1。以下，進一步詳細說明。
Hereinafter, a method of manufacturing a multilayer ceramic capacitor using the above conductive paste will be described. First, on the
首先，準備未燒成之陶瓷片的陶瓷生片。該陶瓷生片方面，可列舉例如：將鈦酸鋇等之既定的陶瓷原料粉末中加入有聚乙烯丁醛等之有機黏合劑與萜品醇等之溶劑而得的介電質層用糊，在PET膜等之支撐膜上塗成片狀，並使其乾燥而去除溶劑者等。而且，包含陶瓷生片之介電質層的厚度並無特別限定，惟由要求積層陶瓷電容器之小型化的觀點而言，係以0.05μm以上3μm以下為佳。 First, a ceramic green sheet of an unfired ceramic sheet is prepared. The ceramic green sheet includes, for example, a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate. It is coated on a supporting film such as a PET film and dried to remove the solvent. The thickness of the dielectric layer including the ceramic green sheet is not particularly limited, but from the viewpoint of miniaturization of multilayer ceramic capacitors, it is preferably 0.05 μm or more and 3 μm or less.
其次，對於在該陶瓷生片之單面藉由網版印刷法等之習知方法，將上述導電性糊印刷、塗布，形成包含導電性糊之內部電極層11者，準備複數片。而且，包含導電性糊之內部電極層11的厚度，由要求該內部電極層11之薄層化的觀點而言，以乾燥後成為1μm以下者為佳。
Next, a plurality of sheets are prepared for printing and coating the conductive paste on one side of the ceramic green sheet by a conventional method such as a screen printing method to form the
接著，除了將陶瓷生片由支撐膜剝離，並使包含陶瓷生片之介電質層12與在該單面形成之包含導電性糊的內部電極層11交替配置之方式積層後，經由加熱/加壓處理而得到積層體10。而且，可作成在積層體10之兩面，進一步配置未塗布導電性糊之保護用的陶瓷生片之構成。
Next, in addition to peeling the ceramic green sheet from the supporting film, and laminating the
接著，將積層體裁成既定大小，形成生片後，對該生片施行黏合劑脫除處理，在還原環境下進行燒成，藉此製造積層陶瓷燒成體。另外，黏合劑脫除處理中之環境，以在大氣或氮氣環境中為佳。進行黏合劑脫除處理時之溫度，例如為200℃以上400℃以下。而且，在進行黏合劑脫除處理時之上述溫度的保持時間係以0.5小時以上24小時以下者為佳。而且，燒成係為了抑制內部電極層中使用之金屬的氧化而在還原環境下進行，又，進行積層體之燒成時的溫度係例如1000℃以上1350℃以下，進行燒成時的溫度之保持時間係例如0.5小時以上8小時以下。 Next, the laminated body is cut into a predetermined size, and after the green sheet is formed, the green sheet is subjected to a binder removal process and fired in a reducing environment to produce a laminated ceramic fired body. In addition, the environment in the adhesive removal process is preferably in the atmosphere or nitrogen environment. The temperature when the adhesive removal treatment is performed is, for example, 200°C or more and 400°C or less. In addition, the retention time of the above-mentioned temperature during the adhesive removal treatment is preferably 0.5 hour or more and 24 hours or less. In addition, the firing is performed in a reducing environment in order to suppress the oxidation of the metal used in the internal electrode layer, and the temperature at which the laminate is fired is, for example, 1000°C or more and 1350°C or less. The holding time is, for example, 0.5 hour or more and 8 hours or less.
藉由進行生片之燒成，則生片中之有機黏合劑可完全去除，同時陶瓷之原料粉末被燒成，而形成陶
瓷製之介電質層12。又，在去除內部電極層11中之有機載體的同時，鎳粉末或以鎳為主成分之合金粉末經燒結或熔化成為一體而形成內部電極，介電質層12與內部電極層11以複數片交替積層而形成積層陶瓷燒成體。而且，在提高在介電質層的內部捕集氧的可靠性的同時，由抑制內部電極的再氧化之觀點而言，可對燒成後之積層陶瓷燒成體施行退火處理。
By firing the green sheet, the organic binder in the green sheet can be completely removed, and the raw material powder of the ceramic is fired to form a ceramic
然後，藉由對所製作的積層陶瓷燒成體設置1對外部電極20，製造積層陶瓷電容器1。例如：外部電極20具有外部電極層21及鍍敷層22。外部電極層21係與內部電極層11電性連接。而且，外部電極20之材料方面，例如可適當地使用銅、鎳或該等之合金。另外，電子零件亦可使用積層陶瓷電容器以外之電子零件。
Then, by providing a pair of
以下，根據實施例與比較例以詳細地說明本發明，惟本發明並不受實施例所限定。 Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited by the examples.
將導電性糊製造完成時、室溫(25℃)下靜置60天後之各試樣之黏度以下述方法測定，以製造完成時之黏度為基準(0%)時，求得各靜置後之試樣黏度之變化量以百分比(%)表示之值([(靜置60天後之黏度-製造完成時之黏度)/製造完成時之黏度]×100)。而且，導電性糊之黏度的變化量係以小者為佳。 When the conductive paste is manufactured, the viscosity of each sample after 60 days of standing at room temperature (25°C) is measured by the following method. When the viscosity at the completion of the manufacturing is used as the reference (0%), the standing The change in the viscosity of the subsequent sample is expressed as a percentage (%) ([(viscosity after standing for 60 days-viscosity at completion of manufacture)/viscosity at completion of manufacture]×100). Moreover, the smaller the change of the viscosity of the conductive paste is better.
導電性糊之黏度：使用Brookfield公司製造之B型黏度計，以10rpm(剪切速率=4sec-1)之條件測定。 Viscosity of conductive paste: Measured under the condition of 10rpm (shear rate=4sec -1 ) using a B-type viscometer manufactured by Brookfield Company.
導電性粉末方面，係使用鎳粉末(粒徑0.3μm)或鎳粉末(粒徑0.2μm)。 As for the conductive powder, nickel powder (particle size: 0.3 μm) or nickel powder (particle size: 0.2 μm) is used.
陶瓷粉末方面，係使用鈦酸鋇(BaTiO3；粒徑0.06μm)。 For ceramic powder, barium titanate (BaTiO 3 ; particle size 0.06 μm) is used.
黏合劑樹脂方面，係使用乙基纖維素。 For the binder resin, ethyl cellulose is used.
呈示表1中使用之分散劑。 The dispersants used in Table 1 are shown.
(1)作為分子量500以下之具有分支烴鏈的酸系分散劑A，使用下述通式(1)(R1=C17H35)所示之酸系分散劑(表1：No.1)。分支鏈的有無係使用1H-NMR之光譜及傅立葉轉換型紅外光譜儀(FT-IR)進行確認。由該等結果可確認到：觀察不到以直鏈分支鏈(直鏈烴基)檢測之波峰，可觀察到末端呈現甲基(-CH3)之波峰，R1具有1以上之分支。 (1) As an acid-based dispersant A having a branched hydrocarbon chain with a molecular weight of 500 or less, an acid-based dispersant represented by the following general formula (1) (R 1 =C 17 H 35 ) (Table 1: No. 1) ). The presence or absence of branched chains was confirmed using 1 H-NMR spectroscopy and Fourier transform infrared spectroscopy (FT-IR). From these results, it was confirmed that no peaks detected by linear branched chains (linear hydrocarbon groups) were observed, but peaks of methyl groups (-CH 3 ) were observed at the ends, and R 1 had 1 or more branches.
(2)作為分子量500以下之具有直鏈烴鏈的酸系分散劑，係使用油酸(C18H34NO2)、硬脂酸(C18H36O2)、二十二酸(C22H44O2)、油醯基肌胺酸(C21H39NO3)、月桂酸(C12H24O2)、亞麻油酸(C18H32O2)、棕櫚油酸(C16H30O2)(表1：No.2~8)。 (2) As an acid-based dispersant with a linear hydrocarbon chain with a molecular weight of 500 or less, oleic acid (C 18 H 34 NO 2 ), stearic acid (C 18 H 36 O 2 ), and behenic acid (C 22 H 44 O 2 ), oleyl sarcosine (C 21 H 39 NO 3 ), lauric acid (C 12 H 24 O 2 ), linoleic acid (C 18 H 32 O 2 ), palmitoleic acid (C 16 H 30 O 2 ) (Table 1: No. 2~8).
(3)作為鹼系分散劑，係使用肉荳蔻基胺、鯨蠟基胺、硬脂基胺(表1：No.9~11)。 (3) As the alkaline dispersant, myristylamine, cetylamine, and stearylamine were used (Table 1: No. 9 to 11).
有機溶劑係使用萜品醇。 Terpineol is used as an organic solvent.
相對於導電性粉末之鎳粉末100質量份，將陶瓷粉末5.3質量份、酸系分散劑A 0.1質量份、黏合劑 樹脂5質量份與有機溶劑49質量份混合，製作導電性糊。將所製作之導電性糊的黏度(60天後)以上述方法評定。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 With respect to 100 parts by mass of nickel powder as conductive powder, 5.3 parts by mass of ceramic powder, 0.1 part by mass of acid-based dispersant A, and binder 5 parts by mass of resin and 49 parts by mass of organic solvent were mixed to prepare a conductive paste. The viscosity (after 60 days) of the produced conductive paste was evaluated by the above method. The evaluation results of the amount of change in the paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為0.5質量份以外，與實施例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 A conductive paste was produced in the same manner as in Example 1, except that the content of the acid-based dispersant A was 0.5 parts by mass. The evaluation results of the amount of change in the paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為1.0質量份以外，與實施例1相同，製作導電性糊。將使用之分散劑的特徵與糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 A conductive paste was produced in the same manner as in Example 1, except that the content of the acid-based dispersant A was 1.0 part by mass. The evaluation results of the characteristics of the dispersant used and the change in the paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為1.5質量份以外，與實施例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 Except that the content of the acid-based dispersant A was 1.5 parts by mass, the conductive paste was produced in the same manner as in Example 1. The evaluation results of the amount of change in paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為2.0質量份以外，與實施例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 Except that the content of the acid-based dispersant A was 2.0 parts by mass, a conductive paste was produced in the same manner as in Example 1. The evaluation results of the amount of change in paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了以油酸(表1：No.2、無烴基之分支)作為酸系分散劑以外，與實施例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 A conductive paste was produced in the same manner as in Example 1, except that oleic acid (Table 1: No. 2, branch without hydrocarbon group) was used as the acid-based dispersant. The evaluation results of the amount of change in paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了酸系分散劑(油酸)之含量分別為0.5質量份(比較例2)、1質量份(比較例3)、1.5質量份(比較例4)以外，與比較例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 Except that the content of the acid-based dispersant (oleic acid) is 0.5 parts by mass (Comparative Example 2), 1 part by mass (Comparative Example 3), and 1.5 parts by mass (Comparative Example 4), it is the same as Comparative Example 1 to produce conductivity paste. The evaluation results of the amount of change in paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
除了分別以硬脂酸(比較例5)、二十二酸(比較例6)、油醯基肌胺酸(比較例7)、月桂酸(比較例8)、亞麻油酸(比較例9)及棕櫚油酸(比較例10)作為酸系分散劑以外，與實施例1相同，製作導電性糊。將糊黏度之變化量的評定結果，與相對於鎳粉末100質量份之酸系分散劑的含量一併呈示於表2。 In addition to stearic acid (comparative example 5), behenic acid (comparative example 6), oleyl sarcosine (comparative example 7), lauric acid (comparative example 8), linoleic acid (comparative example 9) Except that palmitoleic acid (Comparative Example 10) was used as an acid-based dispersant, a conductive paste was produced in the same manner as in Example 1. The evaluation results of the amount of change in the paste viscosity are shown in Table 2 together with the content of the acid-based dispersant relative to 100 parts by mass of the nickel powder.
相對於作為導電性粉末之鎳粉末(粒徑：0.3μm)100質量份，將陶瓷粉末11.6質量份、分散劑0.6質量份(酸系分散劑A 0.2質量份與鹼系分散劑0.4質量份)、黏合劑樹脂5質量份與有機溶劑51質量份混合，製作導電性糊。而且，鹼系分散劑方面，係使用肉荳蔻基胺(表1：No.9)。將製作之導電性糊的黏度變化量(60天後)以上述方法評定。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 With respect to 100 parts by mass of nickel powder (particle size: 0.3μm) as conductive powder, 11.6 parts by mass of ceramic powder and 0.6 parts by mass of dispersant (0.2 parts by mass of acid dispersant A and 0.4 parts by mass of alkali dispersant) , Mix 5 parts by mass of binder resin and 51 parts by mass of organic solvent to make a conductive paste. In addition, for the alkaline dispersant, myristylamine was used (Table 1: No. 9). The viscosity change (after 60 days) of the produced conductive paste was evaluated by the above method. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為0.5質量份以外，與實施例6相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 A conductive paste was produced in the same manner as in Example 6, except that the content of the acid-based dispersant A was 0.5 parts by mass. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了酸系分散劑A之含量為2.0質量份以外，與實施例6相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 A conductive paste was produced in the same manner as in Example 6, except that the content of the acid-based dispersant A was 2.0 parts by mass. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了陶瓷粉末之含量為5.3質量份以外，與實施例7相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 A conductive paste was produced in the same manner as in Example 7 except that the content of the ceramic powder was 5.3 parts by mass. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了使用鎳粉末(粒徑：0.2μm)，並以肉荳蔻基胺(實施例10)、鯨蠟基胺(實施例11)及硬脂基胺(實施例12)作為鹼系分散劑，且鹼系分散劑之含量為0.5質量份以外，與實施例9相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 In addition to using nickel powder (particle size: 0.2μm), and using myristylamine (Example 10), cetylamine (Example 11) and stearylamine (Example 12) as alkaline dispersants, and Except that the content of the alkali-based dispersant was 0.5 parts by mass, the same procedure as in Example 9 was used to prepare a conductive paste. The evaluation results of the paste viscosity are shown in Table 3 together with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 indicates the amount relative to 100 parts by mass of the nickel powder.
除了使用油酸0.3質量份(比較例11)、硬脂酸0.3質量份(比較例12)作為酸系分散劑以外，與實施例6相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 A conductive paste was produced in the same manner as in Example 6, except that 0.3 parts by mass of oleic acid (Comparative Example 11) and 0.3 parts by mass of stearic acid (Comparative Example 12) were used as the acid-based dispersant. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了使用油酸作為酸系分散劑以外，與實施例11相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 A conductive paste was produced in the same manner as in Example 11 except that oleic acid was used as an acid-based dispersant. The evaluation results of the paste viscosity are shown in Table 3 along with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 represents the amount relative to 100 parts by mass of the nickel powder.
除了使用硬脂酸作為酸系分散劑以外，與實施例12相同，製作導電性糊。將糊黏度之評定結果，與鎳粉末之粒徑、分散劑及陶瓷粉末之含量一併呈示於表3。另外，表3中之含量(質量份)係表示相對於鎳粉末100質量份之量。 Except for using stearic acid as the acid-based dispersant, a conductive paste was produced in the same manner as in Example 12. The evaluation results of the paste viscosity are shown in Table 3 together with the particle size of the nickel powder, the content of the dispersant and the ceramic powder. In addition, the content (parts by mass) in Table 3 indicates the amount relative to 100 parts by mass of the nickel powder.
實施例之導電性糊係，相較於任意比較例之導電性糊，經60天後之糊黏度的變化量較小。因此，包含分子量500以下之具有分支烴鏈的酸系分散劑之導電性糊，顯示具有良好的黏度安定性。 Compared with the conductive paste of any comparative example, the conductive paste of the example has a smaller change in the viscosity of the paste after 60 days. Therefore, a conductive paste containing an acid-based dispersant having a branched hydrocarbon chain with a molecular weight of 500 or less exhibits good viscosity stability.
本發明之導電性糊係經時性黏度安定性非常優異，特別是適合作為行動電話、數位機器等之電子機器之片零件的積層陶磁電容器的內部電極用之原料來使用。 The conductive paste of the present invention has excellent viscosity stability over time, and is particularly suitable for use as a raw material for internal electrodes of multilayer ceramic capacitors that are chip parts of electronic devices such as mobile phones and digital devices.
1‧‧‧積層陶瓷電容器 1.‧‧Multilayer ceramic capacitors
10‧‧‧陶瓷積層體 10‧‧‧Ceramic laminated body
11‧‧‧內部電極層 11‧‧‧Internal electrode layer
12‧‧‧介電質層 12‧‧‧Dielectric layer
20‧‧‧外部電極 20‧‧‧External electrode
21‧‧‧外部電極層 21‧‧‧External electrode layer
22‧‧‧鍍敷層 22‧‧‧Plating layer
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| WO2019043674A2 (en) * | 2017-08-30 | 2019-03-07 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| JP6546309B1 (en) * | 2018-03-19 | 2019-07-17 | 株式会社ノリタケカンパニーリミテド | Conductive paste with stable viscosity over time |
| JP7206671B2 (en) * | 2018-07-25 | 2023-01-18 | 住友金属鉱山株式会社 | Conductive paste, electronic parts and laminated ceramic capacitors |
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| KR102741316B1 (en) * | 2018-10-31 | 2024-12-12 | 쇼에이 가가쿠 가부시키가이샤 | Ni paste and multilayer ceramic capacitors |
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| MY209100A (en) * | 2018-12-25 | 2025-06-21 | Sumitomo Metal Mining Co | Conductive paste, electronic component, and laminated ceramic capacitor |
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| JP2012226865A (en) * | 2011-04-15 | 2012-11-15 | Sumitomo Metal Mining Co Ltd | Conductive paste composition |
| TW201426778A (en) * | 2012-12-26 | 2014-07-01 | Nuri Vista Co Ltd | Paste for internal electrode and multi-layer ceramic capacitor using the same |
| TW201541469A (en) * | 2014-03-20 | 2015-11-01 | Sekisui Chemical Co Ltd | Electroconductive paste |
| JP2015216244A (en) * | 2014-05-12 | 2015-12-03 | 株式会社村田製作所 | Conductive paste and ceramic electronic part |
| TW201606007A (en) * | 2014-07-31 | 2016-02-16 | 住友金屬鑛山股份有限公司 | Conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108780673B (en) | 2020-06-02 |
| JP6635186B2 (en) | 2020-01-22 |
| CN108780673A (en) | 2018-11-09 |
| JPWO2017150438A1 (en) | 2019-01-31 |
| WO2017150438A1 (en) | 2017-09-08 |
| KR20180117121A (en) | 2018-10-26 |
| TW201805954A (en) | 2018-02-16 |
| KR102647944B1 (en) | 2024-03-14 |
| MY188260A (en) | 2021-11-24 |
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